Name: Vaidish Sumaria

Andrew ID: vsumaria

Date: September 22, 2016

Report Assignment 2
Reaction Path Synthesis: Solvay Process
Reaction Path Synthesis:
The direct reaction of Calcium carbonate with Salt is non-spontaneous. Sodium chloride does not react
with Calcium carbonate to any significant degree at any temperature because of unfavorable equilibrium.
Thus in order to achieve overall reaction goal, the reaction needed to be broken up into series of sub steps,
some with additional substances. These sub steps would be spontaneous is nature ( G<0 .
This method of converting a non-spontaneous process to a spontaneous process using many different substeps is called Reaction Path Synthesis.
In the Solvay process, as described above, the reaction conditions (Temperature) of the sub-reactions is
kept such that all the reactions have ( G<0 i.e. they are all spontaneous.

Solvay Process:
The overall reaction can be regarded as between Calcium Carbonate and Sodium Chloride:

CaC O3 ( s ) +2 NaCl ( aq ) CaC l 2 ( aq ) + Na2 C O 3 ( aq)

This reaction is endothermic reaction ( H=+20 kJ mol

and has a Gibbs free energy change

G=60 kJ mol1 . As the G>0 therefore the reaction is not spontaneous (Equilibrium lies well
to the left). So the production of Sodium Carbonate must be undertaken by an indirect route. The product
is obtained by a series of seven stages.
The process is known as the ammonia-soda process or the Solvay process, names after the Belgian
industrial chemist who patented it in 1861.
The various stages of the Solvay process are interlinked as can be seen from the diagram and description
below:

Figure 1: Different Stages of the Solvay Process

(All thermodynamic calculations are done assuming the

and

values

independent of temperature).
1. Ammoniation of Brine:
Ammonia gas is absorbed in concentrated brine to give a solution containing both sodium
chloride and ammonia. Na+(aq), Cl-(aq), NH4+(aq), OH-(aq) ions and NH3(aq) are present.
2. Formation of Calcium oxide and Carbon dioxide:
Kilns are fed with a limestone/coke mixture (13:1 by mass). The coke burns in a counter-current
of pre-heated air:

C ( s ) +O2 ( g ) C O2 ( g )
Reaction Thermodynamics:

H rxn= ni H p n i H r

CO
( 2(g))
O
( 2(g))
1 H f (C , s graphite)+1 H f
1 H f
H rxn =
[ 1 (393.51 ) ][ 1 ( 0 ) +1 ( 0 ) ] =393.51 kJ mol1

Srxn= ni S p ni S r
CO
( 2( g))
O
( 2( g))
1 S f (C , s graphite)+1 S f
1 S f
S rxn=
[ 1 ( 213.68 ) ][ 1 ( 5.69 ) +1 ( 205.03 ) ] =2.96
H=393.51 kJ mol1 S=2.96

J
1
mol
K

J
mol1 T =25 =298.15 K
K

G= HT S=394.39 kJ mol1 ( Spontaneous )

The heat of combustion raises the temperature of the kiln and the limestone decomposes:

CaC O3 ( s ) CaO ( s )+C O2 ( g )

Reaction thermodynamics:

H rxn= ni H p n i H r

CO

( 2 ( g ))+1 H f (CaO( s))

CaCO
( 3( s))
1 H f
1 H f
H rxn=
[ 1 (393.51 ) +1(635.13) ] [ 1 (1207.13 ) ]=178.49 kJ mol

Srxn= ni S p ni S r

CO

( 2 ( g ))+1 S f (CaO( s))

CaCO
( 3(s ))
1 S f
1 S f
S rxn=
[ 1 ( 213.68 ) +1(38.2) ][ 1 ( 88.7 ) ] =163.18
H=+178.49 kJ mol1 S=163.18

J
1
mol
K

J
mol1 T =1000 =1273.15 K
K

G= HT S=29.26 kJ mol1 ( Spontaneous )

The gas, containing approximately 40% carbon-dioxide, is freed of the lime dust and sent to the
carbonating (Solvay) towers. The residue, Calcium oxide, is used in ammonia recovery (step 7).

3. The Solvay Tower

This is the key stage in the process. The ammoniated brine from step (1) is passed down through
the Solvay Tower while carbon dioxide from steps (2) and (5) is passed up it. The Solvay Tower
is tall and contains a set of mushroom-shaped baffles to slow down and break up the liquid flow
so that the carbon dioxide can be efficiently absorbed by the solution. Carbon dioxide, on
dissolving, reacts with the dissolved ammonia to form ammonium bicarbonate:

N H 3 ( g ) + H 2 O ( l ) +C O2 ( g ) NH 4 HCO 3 ( aq)

The solution now containing ions Na + (aq), Cl- (aq), NH4+ (aq) and (HCO3)- (aq). Of the four
substances which could be formed by different combinations of these ions, Sodium bicarbonate
(NaHCO3) is the least soluble. It precipitates as a solid in the lower part of the tower, which is
cooled. The net process is:

NaCl ( aq ) + N H 3 ( aq ) + H 2 O ( l ) +C O2 ( g ) Na HCO 3 ( s )+ N H 4 Cl (aq)

Reaction Thermodynamics:

H rxn= ni H p n i H r
NaHCO
NH
( 4 Cl( aq))
NH
H
CO

( 2( g) )
( 2O( l))+ 1 H f
( 3(aq) )+1 H f
1 H f (NaCl ,(aq))+1 H f
( 3(s))+ 1 H f
1 H f
H rxn=
[ 1 (947.68 ) +1(299.66) ] [ 1 (407.25 ) +1 (80.8 ) +1 (285.83 )+1 (393.51 ) ] =79.95 kJ mol1
Srxn= ni S p ni S r

NaHCO
NH
( 4 Cl (aq) )
NH
H
CO

( 2(g) )
( 2 O(l ))+1 S f
( 3(aq))+1 S f
1 S f ( NaCl ,( aq))+1 S f
( 3( s))+1 Sf
1 S f
S rxn=
[ 1 ( 102.09 ) +1(169.87) ] [1 ( 115.48 ) +1 ( 111.3 ) +1 ( 69.91 ) +1 ( 213.68 ) ]=238.41

H=79.95 kJ mol1 S=238.41

J
mol1
K

J
mol1 T =60 =333.15 K
K

1
G= HT S=0.524 kJ mol ( Spontaneous )

A suspension of solid Sodium bicarbonate in solution of Ammonium Chloride is run out of the
base of the tower.
4. Separation of solid Sodium bicarbonate
The suspension is filtered to separate the solid Sodium bicarbonate from the Ammonium chloride
solution, which is used in step (7).
5. Formation of Sodium carbonate:
The sodium bicarbonate is heated in rotating ovens at 450 K so that it decomposes to sodium
carbonate, water and carbon dioxide:

2 NaHC O3 ( s ) Na2 CO3 ( s )+ H 2 O ( g ) +CO2 ( g )

Reaction Thermodynamics:

 H rxn= ni H p n i H r

Na2 CO
H
CO
( 2( g))
2 H f ( NaHC O3 ,(s))
( 2 O(g))+1 H f
( 3(s) )+1 H f
1 H f
H rxn =
[ 1 (1130.94 )+ 1 (241.82 ) +1(393.51) ][ 2 (947.68 ) ] =129.09 kJ mol1
Srxn= ni S p ni S r
Na2 CO
H
CO
( 2( g) )
2 S f ( NaHC O3 ,(s))
( 2 O(g))+1 S f
( 3( s) )+ 1 S f
1 S f
S rxn=
[ 1 ( 135.98 ) +1 ( 188.72 )+ 1 ( 213.68 ) ] [ 2 ( 102.09 ) ]=334.2
H=129.09 kJ mol1 S=334.2

J
mol1
K

J
mol1 T =200 =473.15 K
K

G= HT S=29.036 kJ mol1 ( Spontaneous )

The carbon dioxide is sent back to the Solvay Tower for use in step (3). The product of the
process, anhydrous sodium carbonate, is obtained as a fine white powder known as light sodium
carbonate.

6. Formation of Calcium Hydroxide:

The last two stages, (6) and (7), are concerned with the regeneration of ammonia from
ammonium chloride (made in step 3). The quicklime from step (2) is slaked with excess water
giving milk of lime:

CaO ( s ) + H 2 O ( l ) Ca(OH )2 ( aq )
Reaction Thermodynamics:

H rxn= ni H p n i H r
H
( 2 O(l ))
1 H f (CaO (s ))+1 H f
H rxn=[1 H f (Ca (OH )2 (s ))]
[1(986.09)][1(635.13)+1(285.83)]=65.13 kJ mol1
Srxn= ni S p ni S r
H
( 2O(l))
1 S f (CaO (s ))+1 S f
Srxn=[1 S f (Ca ( OH )2 (s))]
[1(83.39)][1(38.2)+1(69.91)]=24.72 kJ mol1
H=65.13 kJ mol1 S=24.72

J
mol1 T =100 =373.15 K
K

G= HT S=55.91 kJ mol1 ( Spontaneous )

7. Regeneration of Ammonia
This calcium hydroxide suspension is mixed with the ammonium chloride solution left from step
(4) and heated:

2 N H 4 Cl ( aq ) +Ca ( OH )2 ( aq ) CaCl2 ( aq ) +2 NH 3 ( g ) +2 H 2 O ( g )

Reaction Thermodynamics:

H rxn= ni H p n i H r
NH
( 4 Cl (aq))
1 H f (Ca(OH )2(aq))+2 H f
H rxn=[1 H f ( CaCl 2 ( aq ) ) +2 H f ( NH 3 ( g )) +2 H f ( H 2 O ( l ) ) ]
[ 1 (795.8 ) +2 (285.83 ) +2 (46.11 ) ][ 1 (1002.81 )+ 2 (299.65 ) ]=142.43 kJ
Srxn= ni S p ni S r

NH
( 4 Cl (aq))
1 Sf (Ca(OH )2 (aq))+ 2 S f
Srxn=[1 S f ( CaCl 2 ( aq ) ) +2 S f ( NH 3 ( g ) ) +2 S f ( H 2 O (l ) ) ]
[ 1 ( 104.6 )+2 ( 69.91 ) +2 (192.34 ) ][ 1 (74.64 ) +2 (169.87 ) ] =364

H=142.43 kJ S=364

J
T=120=393.15 K
K

G= HT S=0.6766 kJ ( Spontaneous )

Complete Recycling of all the intermediates

J
K

Figure 2: Solvay process for the production of soda ash as an example of a closed production circle in chemical industry (green
= reactants, black = intermediates, red = products)

Figure 2 describes the Solvay process where all the intermediates substances used in the process are
regenerated within the process and recycled. So if we have an 100% efficiency, the only two products of
the whole process would be Calcium Chloride and Sodium bicarbonate.

Process Conditions to overcome Unfavorable Thermodynamics:

Overall reaction of ammoniation of brine and then treatment of Carbon-dioxide to ammoniated brine is as
under:

NaCl+ N H 3+ H 2 O+C O 2 Na HCO3 + N H 4 Cl

The above reaction shows the role of ammonia and Carbon-dioxide in the process, and also determines
the yield of the final product. There so conditions favorable to it are precisely defined. For these the
reaction is divided in to two steps:

N H 3+ H 2 O+C O 2 N H 4 HC O3 ..(a)

NaCl+ N H 4 HC O3 2 NaHC O 3 + N H 4 Cl .(b)

Reaction (a) is undoubtedly favored by low temperature because it requires the dissolution of gas in
water, is displaced to right by virtue of the fact that reaction (b), which utilizes the product by subtracting
it from (a) is displaced in the same direction. Consequently, it is the precipitation of NaHCO 3 according to
(b) which is the driving force behind the entire method.
Temperature
NaCl
357
358.5
359

0 C
20 C
30 C

NH4HCO3
120
217
269

Solubility in gm/L
NH4Cl
298
374
467

NaHCO3
69
95.4
109

Above data indicate that precipitation fortunately tends to take place preferentially with satisfactory
yields. On the basis of data and common ion effect on precipitation of salts, physiochemical conditions
most suitable for the forward step of reaction (b) which causes precipitation of NaHCO 3 are as under.

To maintain lowest possible temperature in order to lower the solubility of Sodium bicarbonate.
To maintain the greatest possible concentration of one or both the salts appearing in the product
side of reaction (b) with the aim of lowering still further solubility of Sodium bicarbonate.

These conditions are nevertheless discerningly applied because they serve to bring about appreciable
increase in the yields of NaHCO 3 and permit the most effective use of costliest reagent NH 4HCO3 in
reaction (b).
Attention is paid to the fact that, if precipitation temperature is always kept low, the sodium bicarbonate
separates in a microcrystalline form which is difficult to filter and it is soluble during subsequent washing
on the filter, increase requirement of NaCl.
Experimentally, the conditions which are most effectively reconcile the physiochemical aspect of
precipitation of sodium bicarbonate economically are as under:

284 gm/L (4.9 mole/L) of NaCl reacting with 76 gm/L (4.5 mole/L) of NH 3 instead of
equimolecular solution of two reagents.
Relatively high temperature (60-65 C) at the start so as to allow the formation of welldeveloped NaHCO3 crystallization seeds and increasing the volume of these seeds to
decrease the solubility of salt with gradual cooling.

References:

1. http://www.essentialchemicalindustry.org/chemicals/sodium-carbonate.html Accessed on: Sep.

20, 2016.
2. http://nptel.ac.in/courses/103106108/Lecture%209.pdf Accessed on: Sep. 19,2016.
3. Sodium hydrogen Carbonate and Sodium Carbonate, Chemical of the Week, Chemistry 104-2,
www.scifun.org, Oct. 14,2010.
4. Chemical Engineering Science, 1976, Vol. 31, pp. 59-69. Pergamon Press. Printed in Great
Britain.
5. http://depa.fquim.unam.mx/amyd/archivero/Entropia_hidratacion_31783.pdf Accessed on Sep.
21, 2016
6. http://chemistry.about.com/od/chartstables/a/heatoformions.htm Accessed on Sep. 21,2016.